The fact that hair is damaged by a variety of chemical agents resulting in a reduction of both aesthetic and physical quality, is well-known. Most common is the damage caused by bleaching and dyeing operations. Also prevalent is damage resulting from too frequent shampooing or the use of harsh shampooing agents. Too, hair can be adversely affected during permanent waving. Damaged hair is recognized by one or more defects such as brittleness, split ends, scaling, low tensile strength, lack of luster, excessive elasticity, increased porosity, and poor manageability.
Hair damage is perhaps most pronounced as a result of bleaching and dyeing processes, particularly dyeing processes wherein oxidizing agents are used to develop the color of the dye. In bleaching, common agents include ammoniacal peroxide, alkali peroxide or mixtures of these with ammonium or potassium persulfate and the like. In oxidation dyeing, the most commonly practiced form of dyeing at the present time, the oxidizing agent is usually hydrogen peroxide. These are drastic treatments and the damage done to the hair during these treatments is well-recognized. It is also found that the almost inevitable contact of the surrounding skin areas with the bleaching or dyeing agents causes irritation manifested by redness of the skin and often by a burning sensation. While the commonly employed methods described suffer from these deficiencies, they are quite effective and therefore widely used. It is apparent that measures which would allow the continued use of the described procedures with a reduction in the problems associated therewith, would be a valuable contribution to the art.
It has now been found, in accordance with the present invention that damage to the hair resulting from chemical treatment such as with bleaching and dyeing agents can be prevented or retarded by treating the hair with a protective agent which is an organic compound containing two or more polar groups which are separated by at least 15 atoms the majority of which are carbon atoms and preferably containing a cyclic moiety of at least 5 atoms. The treatment of the hair with the protective agent can take place either prior to contact with the damaging agent or concurrently with treatment with the hair damaging agent.
Accordingly, it is an object of the present invention to provide a composition and a process for protecting the hair from degradation and adverse effects caused by treating agents.
It is also an object of the present invention to provide protection to the skin and scalp during hair treatment.
It is a more particular object of this invention to protect the hair during bleaching and oxidation dyeing processes.
Still another object of this invention is to reduce or eliminate the deficiencies exhibited by damaged hair such as split ends, scaling, reduced tensile strength, lack of luster, brittleness, excessive elasticity, and lack of manageability.
Still other objects of this invention will be apparent from the following description and claims.
As already noted, this invention involves the treating of hair either prior to the application of a damaging agent or concurrently with the application of a damaging agent with a protective agent which is an organic compound containing two or more polar groups separated by at least 15 atoms the majority of which are carbon atoms and preferably containing a cyclic moiety of at least 5 atoms. The protective agents are simply applied from aqueous compositions. The concentration of the protective agent can vary widely although a concentration of about 0.1 to 20% by weight of the composition is generally useful. A preferred range for most purposes is about 0.5 to 10% by weight of the composition. As will be seen from the following discussion; compatibility of the protective agents and various compositions should present little problem since a wide variety of protective agents are disclosed including anionic, cationic and non-ionic materials.
As used herein, the term "polar group" is meant to define a group having a dipole moment and containing at least one nitrogen, oxygen, phosphorus, sulfur or combinations thereof. These groups are deemed to be capable of hydrogen bonding with the protein, although the formation of stronger bonds such as covalent bonds is not excluded. The cyclic moiety is preferably a carbocyclic, i.e. cyclic hydrocarbon moiety of 5 to 18 carbon atoms which can be saturated or can contain from 1 to 9 double bonds and can contain one or more substituents on the ring. Heterocyclicmoieties which contain the structures --O--, --S--, --N--, or --NH-- in the ring can also be present in the protective agent and serve as the necessary cyclic moiety.
In accordance with the present invention, it has been discovered that hair damage caused by the contact of chemicals, particularly oxidizing agents can be reduced or eliminated by contacting the hair with the compounds of the general type above either prior to contact with the damaging agent or concurrently with the damaging agent. Rinsing of the hair with water or a mild soap solution after application of the protective agent but prior to the application of the irritant does not cause a significant change in the effect of the protective agent when a damaging agent is subsequently applied. This and other types of evidence, such as electrophoretic studies of mixtures of soluble proteins and protective agents, have shown that some form of interaction occurs between keratin and the protective agent. Although the complex formed between protein molecules and the protective agent can be isolated by the indicated electrophoresis, the specific nature of the complex has not yet been established. It is presumed, however, that both adsorption and some form of chemical interaction are involved. It is further theorized that the cyclic structure which is preferred in the protective agent aids in the adsorption of the agent onto the keratin of the hair and that the polar groups of the protective agent interact with the protein molecules of the keratin.
In addition to the requirement that the protective agent contain at least two polar groups, the polar groups of the protective agent must also be separated by a chain of at least 15 atoms, a majority of which should be carbon atoms. However, the presence of additional polar groups located intermediary to the described two terminal polar groups does not appear to interfere in the protective effect. It is believed that as a result of this chain length, the indicated polar groups are capable of and do interact with different protein molecules. The damaging action of chemicals such as oxidants is believed to be caused by a degradation of the protein molecules. This damage is irreparable and results in brittleness, scaliness, split ends, loss of luster and the like. The protective agents employed in the compositions of the present invention are believed to counteract this breakdown by providing additional bridges between the protein molecules of the keratin layer, which maintain the integrity of the keratin. It is to be understood, however, that we do not wish to be bound by the foregoing explanation of the activity of the protective agents of the present invention, and that such explanation is only set forth for a better understanding of the present invention.
The protective agents of the present invention contain at least two polar groups separated by an organic radical of at least 15 atoms, a majority of which are carbon and which preferably contains a cyclic group. The polar groups should be compatible with the total composition and should be of the type capable of existing in the aqueous phase, i.e. without irreversibly reacting with the water. Additional polar groups may be present in this divalent radical or may be located on branches attached to this radical. Such additional polar groups do not interfere in the effectiveness of the protective agent. The two polar groups described can be the same or different. Suitable polar groups include hydroxyl (--OH); carboxyl (--COOH); ester (R'O--CO--, wherein R' can be aliphatic, cycloaliphatic, or aromatic radical of 1-12 carbon atoms, or can be part of a polyester chain); amino (--NH.sub.2); substituted amino (NHR" or --NR"R'", wherein R" or R'" are aliphatic or aromatic hydrocarbon radicals of 1-12 carbon atoms, or wherein R" and R'" can combine to form 3- to 6-membered rings with the nitrogen, or wherein R" is part of a polyamine chain); amido ##STR1## substituted amido ##STR2## wherein R.sup.IV and R.sup.V are aliphatic or aromatic hydrocarbon radicals of 1-12 carbon atoms and R.sup.IV can be part of a polyamide chain); quaternary ammonium salts ##STR3## where R.sup.VI, R.sup.VII, and R.sup.VIII are lower alkyl radicals and X is an anion such as a halogen ion); sulfate (--SO.sub.4 Me, where Me is a metal and preferably an alkali metal); sulfonate (--SO.sub.3 Me); sulfonamide (--SO.sub.2 NH.sub.2); substituted sulfonamide (--SO.sub.2 NHR.sup.IV or --SO.sub.2 NR.sup.IV R.sup.V); thio acid salts (--COSMe); thioesters ##STR4## sulfoxides (.dbd.SO); sulfonic acid (--SO.sub.3 H); sulfinic acid (--SO.sub.2 H); phosphate (--HMePO.sub.4 or --Me.sub.2 PO.sub.4); and phosphonium salts (--HPO.sub.3 Me). The preferred polar groups employed in the protective agents of the present invention are those which contain, aside from any metal or halogen which may be associated with the polar group in ionic form, carbon and oxygen or carbon and nitrogen. In general, functional groups of greater polarity are preferred over those of lesser polarity. It will be apparent that the size of any of the described substituents and particularly hydrocarbon substituents on the polar groups will affect the polarity. In general, the preferred substituents on the polar groups are lower alkyl groups and such water-solubilizing groups as polyoxyalkylene radicals, in particular polyethylene glycol chains.
The effectiveness of the protective agent in preventing skin irritation not only requires the presence of at least two polar groups in the protective agent, but also the separation of the polar groups by an atom chain of at least 15 atoms, the majority of which are carbon atoms. The presence of additional polar groups does not interfere in the function of the two polar groups separated by the necessary number of atoms, regardless of whether these polar groups are part of such chain or located on side branches of the molecule. The presence of more than two polar groups each of which are separated by 15 or more atoms increases the effectiveness of a protective agent in which the polar groups are weak polar groups, such as hydroxyl groups, but does not appear to add significantly to the effectiveness of a protective agent containing at least two strong polar groups such as carboxyl groups separated by the necessary linking chain.
Although the minimum size of the linking radical is determined by the length of the chain separating the polar groups, the maximum size of the linking radical is determined by the dispersibility of the protective agent in the medium in which it is incorporated. Thus compounds which are not liquid or colloidally dispersible are not suitable in the present invention. Hence, the upper limit of the size of the linking radical is determined not only by the number of atoms in the linking radical, but also by the presence of additional polar groups in the linking radical which can increase the dispersibility of the protective agent, as well as the nature of any radical attached to the polar group. In general, however, the linking radical contains less than 80 atoms. As indicated, the linking radical has, preferably, a carbon backbone structure which can be aliphatic, cycloaliphatic, or aromatic in nature. The required carbocyclic or heterocyclic moiety need not be part of the backbone structure. Particularly effective are hydrocarbon linking radicals which contain a cycloaliphatic or aromatic ring structure. In addition to the preferred hydrocarbon structure, the linking radical can also be in the form of a polymeric structure such as a polyester, polyether, polyamide, or polyamine. Although other polymeric linking radicals will be apparent to those skilled in the art, many of these radicals are excluded by virtue of the limitations with respect to solubility or colloidal dispersibility required to give rise to the protective properties. The preferred polymeric linking radicals are the polyether radicals derivable from polyoxyalkylene ethers, containing 2 to 30 oxyalkylene units in which the alkylene radical contains from 2 to 4 carbon atoms. The polyoxyalkylene units can, in addition, contain ester groups. Thus, suitable linking radicals are obtained by the reaction of a polyoxyalkylene glycol with a polycarboxylic acid.
It is apparent that the protective agent can be present in the compositions in the form of a suitable salt. For instance, protective agents such as dimer acid can be used as the sodium, potassium, ammonium or triethanolamine salt. Other salts appropriate to the particular composition can be used. Similarly, amine group containing protective agents can be used in the salt form. The selection of the appropriate salt is within the skill of the art and will depend on the nature of the other ingredients, solubility and similar considerations.
The following classes of materials are protective agents suitable for use in the present invention.
A. the polymerized product of 2 to 4 molecules of a monomeric C.sub.12 to C.sub.26 fatty acid, said product containing 2 to 4 carboxyl groups; or in place thereof derivative radicals selected from the group consisting of carboxyl salt; hydroxyl; unsubstituted amino; substituted amino wherein the substituents are aliphatic or aromatic hydrocarbon radicals of 1 to 12 carbon atoms, or said substituents taken together form a 3 to 6 membered carbocyclic or heterocyclic ring with the amino nitrogen; unsubstituted amido; substituted amido wherein the substituents are aliphatic or aromatic hydrocarbon radicals of 1 to 12 carbon atoms, or said substituents taken together form a 3 to 6 membered carbocyclic or heterocyclic ring with the amido nitrogen; quaternary ammonium wherein the nitrogen substituents are alkyl of 1 to 6 carbon atoms; lower alkyl ester; sulfate; sulfonate; phosphate; phosphonate; and derivative compounds containing further substituents in said alkyl, aliphatic or aromatic hydrocarbon radicals selected from the group consisting of carboxyl and the said derivative radicals. PA1 R.sub.1 is an aliphatic hydrocarbon group having from 1 to 6 carbon atoms; PA1 X is an anion; PA1 Y is an alkylene radical having 1 to 8 carbon atoms; PA1 m is 3 or 4; PA1 n is 2 or 3; and PA1 p is 0, 1, or 2. PA1 B. esters and polyesters of cycloaliphatic or aromatic polycarboxylic acids containing at least one 5 to 7 carbon ring and polyoxyalkylene ethers containing 2 to 30 oxyalkylene units in which the alkylene radical contains 2 to 4 carbon atoms. The benzene, naphthalene, cyclohexane, cyclopentane, cycloheptane, and diphenyl polycarboxylic acids are suitable. Among the preferred polycarboxylic acids are the benzene, di-, tri-, and tetra-carboxylic acids, the corresponding dihydrobenzene (cyclohexadiene), tetrahydrobenzene (cyclohexene), and cyclohexane polycarboxylic acids. The degree of polymerization can vary widely so long as the requirements that the compounds contain at least 15 atoms between the polar groups and the proper solubility or dispersibility characteristic in aqueous media are maintained. The polyoxyalkylene ether can contain further substituents such as shown in Compounds 47 and 51 in Example 1. PA1 C. esters and polyesters of the polymerized fatty acid defined in A above and a polyol selected from the group consisting of PA1 a. polyoxyalkylene ethers containing 2 to 30 oxyalkylene units in which the alkylene radical contains 2 to 4 carbon atoms; PA1 b. condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, having the general formula: ##STR6## wherein a is 1 to 150 PA1 c. condensation products of alkylene oxides having 2 to 4 carbon atoms and polyamines having 2 to 4 amino groups and containing 2 to 8 carbon atoms in an aliphatic, cycloaliphatic or aromatic group. The alkylene oxide addition units can comprise block or random copolymer units as well as homopolymer units. Specific materials of this type having the following formula have been found to be particularly useful in this invention: ##STR7## where x is 2 to 10 and y is 2 to 15.
Among the cationic protective agents defined in A which can be utilized in this invention are fat polyquaternary ammonium compounds having the formula: ##STR5## in which R is the hydrocarbon radical of the polymeric fat acids, R(COOH).sub.n obtained by polymerization of an unsaturated higher fatty acid containing 12 to 26 carbon atoms;
The polymeric fat acids from which the quaternary ammonium compounds employed as protective agents in the present invention are derived are polymerization products of unsaturated fatty acids containing from 12 to 26 carbon atoms and generally have a degree of polymerization of two to four. Quaternary ammonium compounds prepared from fatty acid mixtures containing such dimer, trimer, or tetramer acids are also useful. Quaternary ammonium compounds of the type useful in the present invention are disclosed in U.S. Pat. Nos. 3,073,864 and 3,299,138, the disclosure of which patents is incorporated herein by reference.
b is 15 to 70 and PA2 c is 1 to 150;
The protective agents described in A, B and C, i.e. those which must contain a cyclic moiety are preferred over those broadly disclosed which do not necessarily contain a cyclic moiety.
As previously indicated, the protective agents are used primarily for the purpose of shielding the hair from the adverse effects of harsh chemicals. No particular effect is seen in restoring hair already damaged. The protective agents do, however, favorably effect the manageability and luster of hair either healthy or damaged. Accordingly, to obtain these benefits as well as to reduce skin irritation, the protective agents are recommended for use in shampoos, hair rinses and the like, particularly where the hair will subsequently be subjected to contact with damaging chemicals such as bleaches and dyes.
The cationic protective agents, especially the class of quaternized polymerized fatty acid amines, mentioned above, are favored in hair rinses. These quaternary compounds can also be advantageously incorporated into a combination shampoo-rinse product if a non-ionic or amphoteric surfactant is used.
It should be mentioned that the presence of protective agent is found to have little or no effect on the basic functions of the compositions in which they are incorporated whether these compositions be bleaches, dyeing compositions, tints, permanent wave solutions, shampoos, grooming preparations or the like.
The following examples are intended to illustrate the nature of the invention more fully but are not to be taken as a limitation on the scope thereof.